EP0000531B1 - Process for the preparation of dialkoxyphosphono alkyl carbamates - Google Patents

Process for the preparation of dialkoxyphosphono alkyl carbamates Download PDF

Info

Publication number
EP0000531B1
EP0000531B1 EP78100416A EP78100416A EP0000531B1 EP 0000531 B1 EP0000531 B1 EP 0000531B1 EP 78100416 A EP78100416 A EP 78100416A EP 78100416 A EP78100416 A EP 78100416A EP 0000531 B1 EP0000531 B1 EP 0000531B1
Authority
EP
European Patent Office
Prior art keywords
formula
group
carbamate
alkyl
alkenylcarbamates
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78100416A
Other languages
German (de)
French (fr)
Other versions
EP0000531A1 (en
Inventor
Hans-Jerg Dr. Kleiner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0000531A1 publication Critical patent/EP0000531A1/en
Application granted granted Critical
Publication of EP0000531B1 publication Critical patent/EP0000531B1/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl

Definitions

  • Dialkoxyphosphonoalkylcarbamates are important as flame retardants for textile goods, especially those based on natural or regenerated cellulose.
  • a technically interesting process for the preparation of these phosphorus-containing products consists in the reaction of dialkyl phosphites with alkenyl carbamates in the presence of peroxides as catalysts (DT-OSen 2024280 and 23 12 090).
  • the dialkyl phosphites in excess, in 2-4 times (DT-OS 2024280) or 1.5-5 times (DT-OS 23 12 090) molar amount - based alkenyl carbamate containing only olefinically unsaturated groups.
  • the peroxidic catalysts are used in amounts of approximately 10-20% by weight, based on the carbamate.
  • dialkyl phosphites of the formula (III) used for the process according to the invention are, for example Dimethyl phosphite, methyl ethyl phosphite, diethyl phosphite, dipropyl phosphite and dibutyl phosphite etc. are used; dimethyl and diethyl phosphite are preferred.
  • alkenyl carbamates (IV) e.g. in question: allyl carbamate, methallyl carbamate, 2-methylbutene - (1) - yl - carbamate, butene - (1) - yl - carbamate, N, N '- ethylene - bis - (allyl carbamate). Allyl and methallyl carbamate, in particular allyl carbamate, are preferred.
  • reaction temperatures are expediently chosen in the interval from approximately 120 ° to 170 ° C., preferably approximately 130 ° to 150 ° C.
  • Peroxide catalysts are e.g. in question: Di - tert. - butyl peroxide, tert. - Buiyl peroxybenzoate, 2,5 - dimethyl bis - 2,5 - (peroxybenzoate), benzoyl peroxide. Surprisingly, tert shows. - Butyl peroxybenzoate a preferred and particularly pronounced catalytic activity.
  • the catalysts are expediently used in an amount of about 1 to 5% by weight, preferably about 2 to 4% by weight, based on the weight of the alkenyl carbamate used.
  • Inert solvents can be used. As such, e.g. Use alcohols and ether.
  • the end product can also be used as a solvent. In general, however, the absence of solvents is used.
  • Nitrogen, argon and carbon dioxide are particularly suitable as such inert gases.
  • the process is expediently and particularly preferably carried out in such a way that the dialkyl phosphite is heated to the required reaction temperature under an inert gas atmosphere and the alkenyl carbamate, mixed with the peroxide, is then metered in.
  • the reaction is complete after 2 to 6 hours.
  • the conversion is then generally over 90% of theory. Th.
  • the starting materials can be reacted in a conventional manner in a different order. However, heating the premixed components together is not recommended, as this can lead to decomposition not only in technical approaches.
  • the process can be carried out batchwise or continuously.
  • any solvents used are distilled off.
  • up to an internal temperature of approx. 120-150 ° C and at a pressure of approx. 0.1 to 5 Torr unreacted parts of the starting materials can be distilled off.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Dialkoxyphosphonoalkylcarbamate besitzen Bedeutung als Flammschutzmittel für Textilgut, insbesondere von solchem auf Basis natürlicher oder regenerierter Cellulose. Ein technisch interessantes Verfahren zur Herstelung dieser phosphorhaltigen Produkte besteht in der Umsetzung von Dialkylphosphiten mit Alkenylcarbamaten in Gegenwart von Peroxiden als Katalysatoren (DT-OSen 2024280 und 23 12 090). Bei diesem Verfahren sollen zur Vermeidung von Nebenreaktionen und zur Verbesserung der Ausbeute die Dialkylphosphite im Überschuss, und zwar in der 2-4fachen (DT-OS 2024280) bzw. 1,5-5fachen (DT-OS 23 12 090) molaren Menge - bezogen auf das jeweils nur olefinisch ungesättigte Gruppe enthaltende Alkenylcarbamat - eingesetzt werden. Demgemäss werden in den Ausführungsbeispielen der DT-OSen die peroxidischen Katalysatoren in Mengen von ca. 10-20 Gew.- %, bezogen auf das Carbamat, verwendet.Dialkoxyphosphonoalkylcarbamates are important as flame retardants for textile goods, especially those based on natural or regenerated cellulose. A technically interesting process for the preparation of these phosphorus-containing products consists in the reaction of dialkyl phosphites with alkenyl carbamates in the presence of peroxides as catalysts (DT-OSen 2024280 and 23 12 090). In this process, in order to avoid side reactions and to improve the yield, the dialkyl phosphites in excess, in 2-4 times (DT-OS 2024280) or 1.5-5 times (DT-OS 23 12 090) molar amount - based alkenyl carbamate containing only olefinically unsaturated groups. Accordingly, in the exemplary embodiments of the DT-OSs, the peroxidic catalysts are used in amounts of approximately 10-20% by weight, based on the carbamate.

Dieses Verfahren hat Jedoch verschiedene Nachteile, insbesondere muss der Überschuss an Dialkylphosphit abdestil-liert werden. Das so zurückgewonnene Phosphit ist aber durch zahlreiche Nebenprodukte verunreinigt, die - wenn überhaupt - nur schwer abtrennbar sind, sodass deswegen die Rentabilität des Verfahrens und damit das Verfahren selbst verbesserungsbedürftig erschien.However, this process has several disadvantages, in particular the excess dialkyl phosphite must be distilled off. However, the phosphite recovered in this way is contaminated by numerous by-products which are difficult, if at all, to separate, so that the profitability of the process and therefore the process itself appeared to be in need of improvement.

Entgegen dem Vorurteil obiger DT-OS, man müsse für die beschriebene Umsetzung das Dialkylphosphit in Überschuss einsetzen, um Nebenreaktionen zu vermeiden, wurde nun gefunden, dass bei einem Molverhältnis von Dialkylphosphit : olefinisch ungesättigte Gruppen in dem Carbamat von 1 : 1 nicht nur Verfahrensprodukte gleicher Qualität und gleicher Ausbeute enhalten werden, wie bei dem bisher bekannten Verfahren, sondern dass diese weniger unerwünschte saure Anteile enthalten, sodass die Säurezahl der Produkte deütlich niedriger liegt. Diese Säurezahl ist für die weitere Veratbeitung - insbesondere die Methylolisierung - von Bedeutung. Während nach der eingangs erwähnten Dt-OS 20 24 280 - siehe deren Beispiele! - dieser Weiterverarbeitung eine Reinigung an einer Aluminiumoxyd-Säure vorgeschaltet werden muss, lassen sich die nach dem erfindungsgemässen Verfahren enthaltenen Produkte direkt weiterverarbeiten.Contrary to the prejudice of the above DT-OS, that the dialkyl phosphite had to be used in excess for the described reaction in order to avoid side reactions, it has now been found that with a molar ratio of dialkyl phosphite: olefinically unsaturated groups in the carbamate of 1: 1, not only process products of the same kind Quality and the same yield are obtained, as in the previously known process, but that they contain less undesirable acidic components, so that the acid number of the products is considerably lower. This acid number is important for further processing - especially methylolization. While according to the aforementioned German OS 20 24 280 - see their examples! - If this further processing has to be preceded by cleaning using an aluminum oxide acid, the products contained by the process according to the invention can be further processed directly.

Gegenstand der Erfindung ist somit ein Verfahren zur Herstellung von Dialkoxyphosphonoalkylcarbamaten der Formel

Figure imgb0001
in der R1 und R2 = gleiche oder verschiedene Alkylreste mit 1-4 C-Atomen,

  • R3 = H oder die CH3-Gruppe,
  • R4 = H, (C1--C4)-Alkyl oder die Gruppe
    Figure imgb0002
    worin A = (C2―C4)-Alkylengruppe,
  • n = 1 oder 2,

durch Umsetzung von Dialkylphosphiten der Formel
Figure imgb0003
in der R1 und R2 die gleiche Bedeutung wie in Formel (I) haben, mit Alkenylcarbamaten der Formel
Figure imgb0004
in der R3 und n die gleiche Bedeutung wie in Formel (I) haben, und
  • R4 = H, (C,-C4)-Alkyl oder die Gruppe
    Figure imgb0005
    worin A, n, und R3 die bei den Formeln (I) und (II) angegebenen Bedeutungen haben,
The invention thus relates to a process for the preparation of dialkoxyphosphonoalkylcarbamates of the formula
Figure imgb0001
 in which R 1 and R 2 = identical or different alkyl radicals with 1-4 C atoms,
  • R 3 = H or the CH 3 group,
  • R 4 = H, (C 1 -C 4 ) alkyl or the group
    Figure imgb0002
     where A = (C 2 ―C 4 ) alkylene group,
  • n = 1 or 2,

by reacting dialkyl phosphites of the formula
Figure imgb0003
 in which R 1 and R 2 have the same meaning as in formula (I), with alkenyl carbamates of the formula
Figure imgb0004
 in which R 3 and n have the same meaning as in formula (I), and
  • R4 = H, (C, -C 4 ) alkyl or the group
    Figure imgb0005
     in which A, n and R 3 have the meanings given in the formulas (I) and (II),

bei erhöhter Temperatur und in Gegenwart von Peroxiden als Katalysatoren, das dadurch gekennzeichnet ist, dass man die Dialkylphosphite (III) und die Alkenylcarbamate (IV) - wenn in diesen R4' = H oder eine (C1-C4)-Alkylgruppe - im Molverhältnis 1 : 1 bzw. - wenn in den Alkenylcarbamaten (IV) R4' = die Gruppe (V) - im Molverhältnis 2 : 1 einsetzt.at elevated temperature and in the presence of peroxides as catalysts, which is characterized in that the dialkyl phosphites (III) and the alkenyl carbamates (IV) - if R 4 '= H or a (C 1 -C 4 ) alkyl group - in a molar ratio of 1: 1 or - if in the alkenyl carbamates (IV) R 4 '= the group (V) - in a molar ratio of 2: 1.

Wenn in den Alkenylcarbamaten (IV) R4' = die Gruppe (V), besitzen diese im Molekül 2 olefinisch ungesättigte Gruppen, sodass in diesem Fall das Molverhältnis Dialkylphosphit : Alkylencarbamat 2 : 1 begrundet ist. Es muss als durchaus überraschend angesehen werden, dass bei dem erfindungsgemässen Verfahren die Umsetzung von 1 Mol Dialkylphosphit mit. 1 Mol olefinisch ungesättigte Gruppen im Alkenylcarbamat durchgeführt werden kann und dabei entgegen den in den DT-OSen 20 24 280 und 23 12 090 geschilderten Nachteilen die Reaktionsprodukte in guten Ausbeuten und befriedigender Reinheit anfallen.If in the alkenyl carbamates (IV) R 4 '= the group (V), they have 2 olefinically unsaturated groups in the molecule, so that in this case the molar ratio of dialkyl phosphite: alkylene carbamate is 2: 1. It must be regarded as quite surprising that in the process according to the invention the reaction of 1 mol of dialkyl phosphite with. 1 mol of olefinically unsaturated groups can be carried out in the alkenyl carbamate and, contrary to the disadvantages described in DT-OSs 20 24 280 and 23 12 090, the reaction products are obtained in good yields and satisfactory purity.

Als Dialkylphosphite der Formel (III) kommen für das erfindungsgemasse Verfahren z.B. Dimethylphosphit, Methyläthylphosphit, Diäthylphosphit, Dipropylphosphit und Dibutylphosphit etc. zum Einsatz; bevorzugt sind Dimethyl und Diathylphosphit.The dialkyl phosphites of the formula (III) used for the process according to the invention are, for example Dimethyl phosphite, methyl ethyl phosphite, diethyl phosphite, dipropyl phosphite and dibutyl phosphite etc. are used; dimethyl and diethyl phosphite are preferred.

Als alkenylcarbamate (IV) kommen z.B. in Frage: Allylcarbamat, Methallylcarbamat, 2 - Methylbuten - (1) - yl - carbamat, Buten - (1) - yl - carbamat, N,N' - Äthylen - bis - (allylcarbamat). Bevorzugt sind Allyl- und Methallylcarbamat, insbesondere Allylcarbamat.As alkenyl carbamates (IV) e.g. in question: allyl carbamate, methallyl carbamate, 2-methylbutene - (1) - yl - carbamate, butene - (1) - yl - carbamate, N, N '- ethylene - bis - (allyl carbamate). Allyl and methallyl carbamate, in particular allyl carbamate, are preferred.

Die Reaktions-Temperaturen werden zweck- mässi,g im Intervall von ca. 120° bis 170° C, vorzugsweise ca. 130° bis 150° C, gewählt.The reaction temperatures are expediently chosen in the interval from approximately 120 ° to 170 ° C., preferably approximately 130 ° to 150 ° C.

Als Peroxid-Katalysatoren kommen z.B. in Frage: Di - tert. - butylperoxid, tert. - Buiyl - peroxybenzoat, 2,5 - Dimethylbis - 2,5 - (peroxybenzoat), Benzoylperoxid. Überraschenderweise zeigt tert. - Butylperoxybenzoat eine bevorzugte und besonders ausgeprägte katalytische Wirksamkeit. Die Katalysatoren werden Zweckmässig in einer Menge von ca. 1 bis 5 Gew.%, vorzugsweise ca. 2 bis 4 Gew.-%, bezogen auf das Gewicht des eingesetzten Alkenylcarbamats, verwendet.Peroxide catalysts are e.g. in question: Di - tert. - butyl peroxide, tert. - Buiyl peroxybenzoate, 2,5 - dimethyl bis - 2,5 - (peroxybenzoate), benzoyl peroxide. Surprisingly, tert shows. - Butyl peroxybenzoate a preferred and particularly pronounced catalytic activity. The catalysts are expediently used in an amount of about 1 to 5% by weight, preferably about 2 to 4% by weight, based on the weight of the alkenyl carbamate used.

Inerte Lösungsmittel können verwendet werden. Als solche finden z.B. Verwendung Alkohole und Äther. Auch das Endprodukt kann als Lösungsmittel verwendet werden. Im allgemeinen wird jedoch in Abwesenheit von Lösungsmitteln gearbeitet.Inert solvents can be used. As such, e.g. Use alcohols and ether. The end product can also be used as a solvent. In general, however, the absence of solvents is used.

Es ist zweckmässig, unter Inertgasschutz zu arbeiten. Als solche Inertgase sind vor allem Stickstoff, Argon, Kohlendioxid geeignet.It is advisable to work under inert gas protection. Nitrogen, argon and carbon dioxide are particularly suitable as such inert gases.

Das Verfahren wird Zweckmässig und besonders bevorzugt derart durchgeführt, dass das Dialkylphosphit unter Inertgasatmosphäre auf die erforderliche Reaktionstemperatur erhitzt und dann das Alkenylcarbamat, vermischt mit dem Peroxid, zudosiert wird. Die Umsetzung ist nach 2 bis 6 Std. beendet. Der Umsatz beträgt dann imm allgemeinen über 90 % d. Th. Die Ausgangsstoffe können in an sich üblicher Weise auch in anderer Reihenfolge zur Umsetzung gebracht werden. Nicht zu empfehlen ist jedoch das gemeinsame Aufheizen der vorgemischten Komponenten, da dies nicht nur bei technischen Ansätzen zu Zersetzungen führen kann.The process is expediently and particularly preferably carried out in such a way that the dialkyl phosphite is heated to the required reaction temperature under an inert gas atmosphere and the alkenyl carbamate, mixed with the peroxide, is then metered in. The reaction is complete after 2 to 6 hours. The conversion is then generally over 90% of theory. Th. The starting materials can be reacted in a conventional manner in a different order. However, heating the premixed components together is not recommended, as this can lead to decomposition not only in technical approaches.

Das Verfahren kann sowohl diskontinuierlich als auch kontinuierlich durchgeführt werden. Zur Reinigung der erhaltenen Reaktionsprodukte werden gegebenenfalls verwendete lösungsmittel abdestilliert. Weiterhin können bis zu einer Innentemperatur von ca. 120-150° C und bei einem Druck von ca. 0,1 bis 5 Torr nicht umgesetzte Anteile an den Ausgangsstoffen abdestilliert werden. Häufig ist jedoch selbst diese einfache Massnahme für die Weiterverarbeitung nicht erforderlich. Die Produkte des erfindungsgemässen Verfahrens sind dann in ihrer Reinheit dan nach dem Verfahren der DT-OSen 20 24 280 und 23 12 090 heregestellten Produkten bei sonst gleichen Eigenschaften dadurch überlegen, dass sie darüber hinaus deutlich weniger saure Anteile (Säurezahl = mg zur Neutralisation von 1 g Substanz notige KOH : ca. 10-15, gegenüber ca. 30-40 der Produkte nach den genannten DT-OSen) enthalten, was für den Einsatz in der Praxis sehr erwünscht ist. Sie können ohne weitere Reinigungsmassnahmen zur Herstellung von Mitteln zur Flammhemmung verwendet werden.The process can be carried out batchwise or continuously. To purify the reaction products obtained, any solvents used are distilled off. Furthermore, up to an internal temperature of approx. 120-150 ° C and at a pressure of approx. 0.1 to 5 Torr unreacted parts of the starting materials can be distilled off. However, even this simple measure is often not required for further processing. The purity of the products of the process according to the invention is then superior to that of products manufactured according to the method of DT-OSs 20 24 280 and 23 12 090 with otherwise the same properties in that they also have significantly less acidic fractions (acid number = mg for neutralizing 1 g substance required KOH: approx. 10-15, compared to approx. 30-40 of the products according to the DT-OSen mentioned), which is very desirable for use in practice. They can be used to produce flame retardants without further cleaning measures.

Die folgenden Beispiele sollen die Erfindung näher erläutern, ohne sie jedoch zu begrenzen.The following examples are intended to explain the invention in greater detail without, however, limiting it.

Beispiel 1example 1

220 g Dimethylphosphit werden unter Stickstoffatmosphare und bei lebhaften Rühren auf 140-1450 C erhitzt. Dann wird ein Gemisch von 202 g Allylcarbamat und 6 g tert.-Butyl- peroxybenzoat innerhalb von 5 Std. eingetropft. Es wird 1 Std. bie 140-1450 C nachgerührt. Anschliessend wird bei 1-2 Torr bis zu einer Innentemperatur von 140° C andestilliert. Dabei destillieren 11 g ab. Es verbleiben ca. 400 g 3 - Dimethoxyphosphonopropylcarbamat. Das entspricht einer Ausbeute von ca. 95 % d. Th.220 g of dimethyl phosphite are heated under a nitrogen atmosphere and vivid stirring at 140-145 0 C. A mixture of 202 g of allyl carbamate and 6 g of tert-butyl peroxybenzoate is then added dropwise within 5 hours. It is 1 hour. Bie 140-145 0 C stirred. The mixture is then distilled at 1-2 torr up to an internal temperature of 140 ° C. Distill off 11 g. About 400 g of 3-dimethoxyphosphonopropyl carbamate remain. This corresponds to a yield of approx. 95% of theory. Th.

Beispiel 2Example 2

220 g Dimethylphosphit werden unter Stickstoffatmosphäre und bei lebhaftem Rühren auf 150-1550 C erhitzt. Dann wird ein Gemisch von 202 g Allylcarbamat und 6 g tert.-Butyl- peroxybenzoat innerhalb von 2,5 Std. eingetropft. Es wird 1 Std. bei 150° C nachgerührt. Anschliessend wird bei 0,8 bis 1,5 Torr bis zu einer Innentemperatur von 140° C andestilliert. Dabei destillieren 5 g ab. Es verbleiben 410 g 3 - Dimethoxyphosphonopropylcarbamat. Das entspricht einer Ausbeute von über 95 % d. Th.220 g of dimethyl phosphite are heated under nitrogen atmosphere and at 0 C with vigorous stirring to 150-155. A mixture of 202 g of allyl carbamate and 6 g of tert-butyl peroxybenzoate is then added dropwise over the course of 2.5 hours. The mixture is stirred at 150 ° C for 1 hour. The mixture is then distilled at 0.8 to 1.5 torr up to an internal temperature of 140 ° C. 5 g distill off. 410 g of 3-dimethoxyphosphonopropyl carbamate remain. This corresponds to a yield of over 95% of theory. Th.

Beispiel 3Example 3

82 g Dimethylphosphit werden unter Stickstoffatmosphäre und bei lebhaftem Rühren auf 140° C erhitzt. Dann wird zunächst während ca. 1.3 Std. ein Gemisch von 60 g Methallylcarbamat und 2,0 g tert.-Butylperoxybenzoat, anschliessend während 40 Min. ein Gemisch von 26 g Methallylcarbamat und 2,0 g tert.-Butyl- peroxybenzoat eingetropft. Es wird 1 Std. bei 135° C nachgerührt. Dann wird bei 0,5-1 Torr andestilliert bis zu einer Innentemperatur von 115° C. Es destillieren 7.5 g ab. Es verbleiben 164 g 3 - Dimethoxyphosphono - 2 - methylpropylcarbamat. Das entspricht einer Ausbeute von ca. 95 % d. Th.82 g of dimethyl phosphite are heated to 140 ° C. under a nitrogen atmosphere and with vigorous stirring. Then a mixture of 60 g of methallyl carbamate and 2.0 g of tert-butyl peroxybenzoate is first added dropwise over a period of about 1.3 hours, then a mixture of 26 g of methallyl carbamate and 2.0 g of tert-butyl peroxybenzoate is added dropwise for 40 minutes. The mixture is stirred at 135 ° C for 1 hour. The mixture is then distilled at 0.5-1 torr to an internal temperature of 115 ° C. 7.5 g distill off. 164 g of 3-dimethoxyphosphono-2-methylpropylcarbamate remain. This corresponds to a yield of approx. 95% of theory. Th.

Beispiel 4Example 4

80g Dimethylphosphit werden unter Stickstoffatmosphäre und bei lebheften Rühren auf 150° C erhitzt. Dann wird ein Gemisch von 94 g 2 - Methylbuten - (1) - yl - carbamat und 4 g Di - tert. - butylperoxid während 2 Std. zugetropft. Anschliessend wird 1 Std: bei 145° C nachgerührt. Dann wird bei 1 Torr bis zu einer Innentemperatur von 140° C andestilliert. Es destillieren 4 g ab. Man erhält 173 g 4 - Dimethyoxyphosphono - 2 - methylbutylcarbamat. Das entspricht einer Ausbeute von über 95 % d. Th.80 g of dimethyl phosphite are heated to 150 ° C. under a nitrogen atmosphere and with stirring. Then a mixture of 94 g of 2-methylbutene (1) yl carbamate and 4 g of di-tert. - Butyl peroxide added dropwise for 2 hours. The mixture is then stirred for 1 hour: at 145 ° C. Then distilled at 1 torr up to an internal temperature of 140 ° C. 4 g distill off. 173 g of 4-dimethyoxyphosphono-2-methylbutylcarba are obtained mat. This corresponds to a yield of over 95% of theory. Th.

Beispiel 5Example 5

99 g Diäthylphosphit werden unter Stickstoffatmosphäre und bei lebhalftem Rühren auf 150° C erhitzt. Dann wird ein Gemisch von 94 g 2 - Methylbuten - (1) ylcarbamat und 3,8 g Di - tert. - butylperoxid während 2 Std. Zugetropft. Anschliessend wird 1 Std. bei 145° C nachgerührt. Dann wird bei 0,6 Torr bis zu einer Innentemperatur von 136° C andestilliert. Es destillieren 3 g ab. Man erhält 192 g 4 - Diäthoxyphosphono - 2 - methylbutylcarbamat. Das entspricht einer Ausbeute von über 95 % d. Th.99 g of diethyl phosphite are heated to 150 ° C. under a nitrogen atmosphere and with live stirring. Then a mixture of 94 g of 2-methylbutene (1) yl carbamate and 3.8 g of di-tert. - Butyl peroxide added dropwise for 2 hours. The mixture is then stirred at 145 ° C for 1 hour. Then distilled at 0.6 Torr to an internal temperature of 136 ° C. 3 g distill off. 192 g of 4-diethoxyphosphono-2-methylbutyl carbamate are obtained. This corresponds to a yield of over 95% of theory. Th.

Beispiel 6Example 6

40 g Dimethylphosphit werden unter Stickstoffatmosphäre und unter lebhaftem Rühren auf 140° C erhitzt. Dann wird ein Gemisch von 45 g Dimethylphosphit, 88 g N,N' - Äthylenbis - (allylcarbamat) und 4 g tert. - Butylperoxybenzoat, das auf 50° C gehalten wird, während 2 Std. eingetropft. Dann wird bei 0,5 Torr bis zu einer Innentemperatur von 145° C andestilliert. Es destillieren 5 g ab. Man erhält 172 g N,N' - Äthylen - bis - (3 - dimethoxyphosphonopropylcarbamat). Das entspricht einer Ausbeute von ca. 95 % d. Th.40 g of dimethyl phosphite are heated to 140 ° C. under a nitrogen atmosphere and with vigorous stirring. Then a mixture of 45 g of dimethyl phosphite, 88 g of N, N '- ethylenebis - (allyl carbamate) and 4 g of tert. - Butyl peroxybenzoate, kept at 50 ° C, added dropwise over 2 hours. Then distilled at 0.5 torr to an internal temperature of 145 ° C. 5 g distill off. 172 g of N, N '- ethylene - bis - (3-dimethoxyphosphonopropylcarbamate) are obtained. This corresponds to a yield of approx. 95% of theory. Th.

Claims (10)

1. Process for the preparation of dialkoxy- phosphonoalkylcarbamates of the formula
Figure imgb0017
in which R, and R2 are identical or different alkyl radicals having from 1 to 4 carbon atoms,
R3 is hydrogen or the CH3 group,
R4 is hydrogen, (C1-4) alkyl or the group
Figure imgb0018
in which A is (C2-4) alkylene,
n is 1 or 2,

by reacting dialkylphosphites of the formula
Figure imgb0019
in which R1 and R2 are.defined as in the formula 1, with alkenylcarbamates of the formula
Figure imgb0020
in which R3 and n are defined as in the formula I and
R'4 is hydrogen, (C1-4)alkyl or the group
Figure imgb0021
In which A, n and R3 are defined as in the formulae I and II, at elevated temperature and in the presence of peroxides as catalysts, which comprises using the dialkylphosphites III and the alkenylcarbamates IV, if R4 is hydrogen or a (C1-4)alkyl group, in a molar ratio of 1 : 1 or, if R'4 in the alkenylcarbamates IV is the group V, in a molar ratio of 2:1.
2. Process as claimed in claim 1, which comprises using as dialkylphosphites of the formula III dimethyl- or diethylphosphite.
3. Process as claimed in claims 1-2, which comprises using as alkenylcarbamates of the formula IV allyl- or methallylcarbamates.
4. Process as claimed in claims 1-3, which comprises using as alkenylcarbamate of the formula IV alkylcarbamate.
5. Process as claimed in claims 1-4, which comprises carrying out the reaction at a temperature of from 120 to 170°C.
6. Process as claimed in claims 1-5, which comprises carrying out the reaction at a temperature of from 130 to 150°C.
7. Process as claimed in claims 1-6, which comprises using as peroxide catalyst tertiary butylperoxybenzoate.
8. Process as claimed in claims 1-7, which comprises using the peroxide catalyst in an amount of from 1 to 5 weight percent, calculated on the alkenylcarbamate IV.
9. Process as claimed in claims 1-8, which comprises using the peroxide catalyst in an amount of from 2 to 4 weight percent, calculated on the alkenylcarbamate IV.
10. Process as claimed in claims 1-9, which comprises heating the dialkylphosphite III to the reaction temperature under an inert gas atmosphere and adding thereafter the alkenylcarbamate IV mixed with the peroxide catalyst.
EP78100416A 1977-07-30 1978-07-18 Process for the preparation of dialkoxyphosphono alkyl carbamates Expired EP0000531B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2734454 1977-07-30
DE2734454A DE2734454C2 (en) 1977-07-30 1977-07-30 Process for the preparation of dialkoxyphosphonoalkyl carbamates

Publications (2)

Publication Number Publication Date
EP0000531A1 EP0000531A1 (en) 1979-02-07
EP0000531B1 true EP0000531B1 (en) 1980-07-23

Family

ID=6015243

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100416A Expired EP0000531B1 (en) 1977-07-30 1978-07-18 Process for the preparation of dialkoxyphosphono alkyl carbamates

Country Status (3)

Country Link
EP (1) EP0000531B1 (en)
DE (2) DE2734454C2 (en)
IT (1) IT1097780B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004019723B4 (en) 2004-04-20 2007-11-29 Knorr-Bremse Systeme für Nutzfahrzeuge GmbH Adjustment device for pneumatically actuated disc brakes and disc brake
FR3003797B1 (en) 2013-03-26 2015-03-13 Saint Gobain FIREPROOF GLAZING

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2312090A1 (en) * 1973-03-10 1974-09-12 Basf Ag POLY-DIALKYLPHOSPHONOALKYLCARBONATES AND THEIR USE FOR FLAME PROTECTION EQUIPMENT OF CELLULOSIC TEXTILES
DE2325576A1 (en) * 1973-05-19 1974-12-05 Bayer Ag DICARBAMIC ACID DIESTER
DE2402174A1 (en) * 1974-01-17 1975-07-31 Bayer Ag Phosphorus-containing dicarbamic acid diesters

Also Published As

Publication number Publication date
IT1097780B (en) 1985-08-31
DE2734454C2 (en) 1979-09-13
IT7826271A0 (en) 1978-07-28
DE2734454B1 (en) 1979-01-04
EP0000531A1 (en) 1979-02-07
DE2860062D1 (en) 1980-11-13

Similar Documents

Publication Publication Date Title
EP0011245B1 (en) Process for the preparation of phosphorus-containing cyanhydrine derivatives and those cyanhydrine derivatives
EP0000531B1 (en) Process for the preparation of dialkoxyphosphono alkyl carbamates
DE1493222A1 (en) Process for the preparation of diorganozinc compounds
DE2437586A1 (en) PROCESS FOR PRODUCING MONOMETHYL TIN TRICHLORIDE
EP0694555A1 (en) Process for the preparation of phosphonic acids esters
EP0090213B1 (en) Process for the preparation of derivatives of vinylphosphonic or vinylpyrophosphonic acids
DE2301789C3 (en) Siloxane-polyoxyalkylene block copolymers, processes for their production and use
DE69402832T2 (en) METHOD FOR PRODUCING BIS (2-BENZOXAZOLYL) STILEN
CH615438A5 (en)
DE2156203A1 (en) PROCESS FOR THE PRODUCTION OF DIALKYL PHOSPHINOXIDES
DE1935313C3 (en) Process for the preparation of 0,0-dimethyl-0-l ^ -dibromo-2 ^ -dichloroethylphosphate
DE2336913A1 (en) Perfluoroalkyl modified monoallyl ethers - surfactants, inters and polymer starting materials
DE808837C (en) Process for the production of acid chlorides of thio- and dithiodiglycolic acids
EP0537197B1 (en) Method for the preparation of phosphonous acid aryl ester halides
DE2516343A1 (en) Aldehyde diacylates contg. phosphorus - prepd. from cpds. contg. phosphorus to hydrogen bonds and unsatd. aldehyde diacylates
DE1090210B (en) Process for the preparation of organosilicon compounds containing phosphonic acid ester residues
EP0272484A2 (en) Process for preparing halogenated phosphono-phosphoric-acid esters and their use
EP0000044B1 (en) Carbamoyloxyalkyl phosphinic acid derivatives, process for their preparation and their use in the preparation of flame-retardant finished materials
EP0011280A1 (en) Process for the preparation of organotin trihalides and their application
EP0071783B1 (en) Process for preparing alkyl or arylthiophosphonic-acid chlorides
DE2619574C3 (en) Process for the preparation of 3-bromopropionic acid amide
DE1140189B (en) Process for the preparation of a saturated fluorocarbon group-containing organosilicon compounds
DE2033987B2 (en) PROCESS FOR THE PREPARATION OF MIXTURES OF DITHIO- AND TRITHIOPHOSPHORIC ACID TRIESTERS
DE1139840B (en) Process for the preparation of trialkyl 9 (10) phosphonostearates
EP0256319A1 (en) S-Butyl-di-n-alkylphosphanes, -phosphaneoxides and phosphanesulphides as well as processes for their preparation

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE CH DE FR GB NL

17P Request for examination filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE CH DE FR GB NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Effective date: 19800723

REF Corresponds to:

Ref document number: 2860062

Country of ref document: DE

Date of ref document: 19801113

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19810718

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19820201

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19820201

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19820501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19830331

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19881117

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT